JPH02140291A - Ori-controlled automobile fuel composition and storage-stable concentrate - Google Patents

Abstract

PURPOSE: To provide the subject composition which shows an anti-sedimentation property and ORI controllability by reacting a specific hydrocarbon dibasic substituted acid anhydride and a specific polyoxyalkylene diamine at a specific ratio.

CONSTITUTION: The objective composition is provided by reacting (A) a hydrocarbon-substituted dibasic acid anhydride [suitable example; a polyisobutenyl succinic acid anhydride shown by formula II (X is 10-30)] shown by formula I (R₁ is a hydrocarbon with a molecular weight of 500-10,000; (y) is 0-3), 1.5-2.5 mole pts. with (B) polyoxyalkylene diamine shown by formula III (R₂, R₃ are each 1-12C alkylene; (q), (r) are 0 or 1; (c) is 2-150; (b)+(d)=2-150; (a)+(e)=0-12), 0.5-1.5 mole pts. at 30-200°C.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel reaction product compositions, ORI inhibited automotive fuel compositions, antifouling and ORI inhibited functional automotive fuel compositions, and anti-sedimentation concentrate formulations for use in automotive fuel compositions. relating to things. More specifically, the present invention provides a composition obtained by reacting a hydrocarbon-substituted dibasic acid anhydride and a polyalkylene diamine, the composition comprising (i)
a hydrocarbon-substituted dibasic acid anhydride and (ii) a polyoxyalkylene diamine, and optionally 02-C+
.

The present invention relates to ORI-suppressed motor fuel compositions comprising a base fuel comprising a reaction product of a hydrocarbon polyolefin polymer/copolymer or a corresponding aminated or hydrogenated polymer/copolymer or a mixture thereof. The present invention also relates to additive concentrates of the above-described components mixed with a hydrocarbon solvent to facilitate the introduction of the concentrate into motor vehicle fuel compositions. Such concentrates are anti-sedimentation properties, which improves the storage stability of the concentrates.

The combustion of hydrocarbon motor fuels in internal combustion engines typically involves
It causes the formation and deposition of deposits on various parts of the combustion chamber as well as the fuel inlet and exhaust system of the engine. The presence of deposits within the combustion chamber greatly reduces the operating efficiency of the engine. First, heat transfer between the combustion chamber and the engine cooling system is inhibited by the build-up of deposits within the combustion chamber. This increases the temperature inside the combustion chamber,
The final gas temperature of the inlet increases. This causes spontaneous ignition of the final gas, causing engine knocking. Furthermore, due to the accumulation of deposits inside the combustion chamber,
The combustion zone capacity is reduced and the engine's compression ratio becomes higher than the designed value. This also causes severe engine knocking. Engine knocking prevents combustion energy from being used effectively. Additionally, prolonged engine knocking can cause stress fatigue and wear and tear on major engine components. The phenomenon described above is characteristic of gasoline-powered internal combustion engines. The above phenomenon has become known as the engine octane requirement increase (ORI) phenomenon, as it is usually overcome by using gasoline with a higher octane rating to run the engine. Therefore, it would be highly advantageous if ORI in an engine could be substantially reduced or eliminated by preventing or mitigating the formation of deposits within the engine's combustion chamber.

Another problem common to internal combustion engines relates to the build-up of deposits within the carburetor, which tends to restrict air flow through the carburetor at idle and at low speeds, causing an overabundance of the combustion mixture. This condition also promotes incomplete combustion of the fuel, causing irregular engine idle link and engine stalling. Excess hydrocarbon and carbon oxide exhaust emissions also occur under these conditions.

Accordingly, it would be desirable to provide a motor fuel composition that minimizes or overcomes the problems described above from an engine operability and overall air quality standpoint.

A third problem common to internal combustion engines is the formation of intake valve deposits. Intake valve deposits interfere with valve sealing and ultimately cause valve combustion. Such deposits interfere with valve operation and sealing, further reducing engine volumetric efficiency and limiting maximum power.

Valve deposits typically result from the formation of thermally and oxidatively unstable fuel or lubricant oxidation products. Hard, carbonaceous deposits build up on the tubes and runners that conduct exhaust gas recirculation (EGR) gas. These deposits are believed to be formed by the rapid cooling of exhaust particles while mixing with the air-fuel mixture. Reduced EGR flow can cause engine knocking and increased NOx emissions. Accordingly, it would be desirable to provide a motor fuel composition that minimizes or overcomes the formation of intake valve deposits.

Various automotive fuel formulations are disclosed that include polyoxyalkylene reaction product additives that minimize the formation of combustion chamber deposits and, therefore, engine ORI. For example, in U.S. Patent Application No. 84,354, filed August 12, 1987, incorporated herein by reference and assigned to the same assignee: A motor fuel composition comprising the reaction product of a polyoxyalkylene diamine, a dianhydride and a hydrocarbon polyamine of Patent Application No. 000,253, and (II) a mixture comprising polyisobutylene ethylene diamine and polyisobutylene in a hydrocarbon solvent. things are disclosed. However, concentrated compositions containing components (I) and (II) precipitated during storage, which was found to be undesirable. Other automotive fuel compositions that include polyoxyalkylene additives to reduce engine ORI include the following, which are described herein by reference.

U.S. patent application Ser. is about 5~
150 and ae has a value of about 2 to 12) are disclosed. Also disclosed are motor fuels containing the novel polyoxyalkylene diamines, alone or in combination with polymer/copolymer additives.

In U.S. Patent Application No. 000,230, filed January 2, 1987, and assigned to the same assignee, the reaction products of polyoxyalkylene diamines, dianhydrides and carbonizations of U.S. Patent Application No. 000,253 are disclosed. Automotive fuel compositions containing hydrogen polyamines are disclosed. In some cases, polymer/copolymer additives having a molecular weight of 500 to 3,500 are also used in combination with such reaction product additives.

U.S. Patent No. 4.659°337, assigned to the same assignee.
No. 2, discloses the use of reaction products of maleic anhydride, polyether polyamines containing oxyethylene and oxypropylene ether components, and hydrocarbon polyamines in gasoline automotive fuels to reduce engine ORI and provide carburetor cleanability. has been done.

U.S. Patent No. 4,659°336, assigned to the same assignee.
No. 1, 2003, a reaction product of a polyether polyamine and a hydrocarbon polyamine containing maleic anhydride, oxyethylene and oxypropylene ether components; is disclosed to reduce engine ORI.

No. 4,631,069, assigned to the same assignee, dibasic acid anhydrides, polyoxyisopropylene of the formula: An alcohol-containing motor fuel composition is disclosed that further includes an antiwear additive that is the reaction product of a diamine and an n-alkyl-alkylene diamine.

No. 4,643,738, commonly assigned to the same assignee, discloses dibasic acid anhydrides of the formula:
A motor fuel composition is disclosed that includes a deposition control additive that is the reaction product of a polyoxyisopropylene diamine (having a value of 50) and an n-alkyl-alkylene diamine.

No. 4,604;103, combustion chamber deposits or increased engine octane demand (ORI)
An automotive fuel anti-fouling additive for use in internal combustion engines is disclosed that maintains the cleanliness of the engine's intake system without imparting oxidation. The disclosed additives have the following formula: %Formula % where R is a hydrocarbon group having from 1 to about 30 carbon atoms; R' is selected from methyl and ethyl;
are integers: R°° and Roo.

are independently hydrogen and -(CH2CHJH1y-H(
where y is an integer from 0 to 5)] is a hydrocarbon polyoxyalkylene polyamine ethane having a molecular weight range of 300 to 2500.

Commonly assigned U.S. Pat. No. 4,581,040 discloses the use of reaction products as antifouling additives in fuel compositions.

The reaction product taught is a maleamide by reacting a fit dibasic acid anhydride with a polyoxyisopropylene diamine of the following formula: The reaction product of the acid, which produces
and (11) polyalkylene acetate (11) producing a condensation product by reacting said maleamic acid with a polyalkylene polyamine (iii) recovering said condensation product. .

Automotive fuel compositions containing amine additives to control precipitation include:

In U.S. Pat. No. 4,357,148, polymers, copolymers or corresponding Automotive fuel additives useful for controlling ORI that are blends of hydrogenated polymers or copolymers are disclosed.

No. 4,166,726 discloses a fuel additive that is a blend of fil alkylphenols, aldehydes, and amimines.

U.S. Patent No. 3,960.515 and U.S. Patent No. 3.8
No. 98.056 discloses the use of mixtures of high and low molecular weight hydrocarbon amines as detergents and dispersants in automotive fuel compositions.

No. 3,438,757 discloses the use of hydrocarbon amines and polyamines in the molecular weight range 450 to 10,000, alone or in combination with lubricating mineral oils, as detergents for automotive fuel compositions. .

It is an object of the present invention to provide a reaction product composition that can be used as an ORI reducing additive in automotive fuel compositions. Another object of the present invention is to provide a method for incorporating the reaction product compositions of the present invention, alone or in combination with the polyolefin polymers/copolymers described herein, into base motor fuel compositions. There is. It is another object of the present invention to provide a motor fuel composition that is anti-deposition and exhibits ORI control properties when used in an internal combustion engine. Yet another object of the invention is to provide a concentrated composition capable of providing the motor fuel composition of the invention in addition to motor fuel.

Combustion chamber deposit formation is minimized while engine O
A reduced RI is a feature of the automotive fuel composition of the present invention. such motor fuel composition is anti-sedimentation;
In particular, it is another feature of the present invention that it exhibits reduced intake valve deposit formation. Incorporating the concentrated composition of the present invention into motor vehicle fuel to minimize the formation of combustion chamber deposits;
It is yet another feature of the present invention that the ORI of the engine can thereby be suppressed.

The automotive fuel composition of the present invention has a reduced engine ORI.
It is an advantage of the present invention to exhibit reduced valve deposit production. It is another advantage of the present invention that the concentrated compositions of the present invention exhibit resistance to precipitation and therefore exhibit improved storage stability.

According to the present invention, the novel reaction products imparting ORI-suppressing properties to automotive fuel compositions are:
carbonization of a hydrocarbon group having a molecular weight of from 0 to 2.500, most preferably from 600 to 1,500, preferably a polypropenyl or polybutenyl group, most preferably a polyisobutenyl group, where y has a value from 0 to 3. 1.5 to 25 mole parts, preferably 2 mole parts, of a hydrogen-substituted dibasic acid anhydride; Fb) of the following formula: C&CH.

CH, CH3 CHs CHs (in the formula, R2
and R8 is a C1-C1□ alkylene group, preferably 0
2-C6 alkylene group, q and r are integers having a value of 0 or 1, preferably q=1. r=0, C is a number from about 2 to 150, preferably 2 to 50, and b+d
is a number from about 2 to 150, preferably from 2 to 50, and a+
e has a value of about 0 to 12, preferably 2 to 8) with 0.5 to 1.5 mole parts, preferably 1 mole part, of a polyoxyalkylene diamine at a temperature of 30 to 200 °C. obtained by.

The automotive fuel composition of the present invention contains 0.0005 to 5.0% by weight, preferably 0.001 to 5.0% by weight of the above-mentioned reaction products.
1.0% by weight, and if used, 02-C1o
2. using a commercially available lead-free base fuel containing 60 PTB, preferably a C2-C6 hydrocarbon polyolefin polymer or copolymer mill. The octane requirement of an OI2 engine (as a function of engine operating time) is compared with the octane requirement of the same engine after it has been disassembled, reassembled, stabilized, and the composition of the invention has been introduced. This is a graph showing the data obtained.

Figure 2 shows the octane demand (as a function of engine operating time) of a Sibosee 2.0°C engine using a commercial unleaded base fuel containing (i1 commercial fuel additive 60 PTB) and (ii
) is a graphical representation of data obtained comparing the octane requirements of the same engine using a motor vehicle fuel composition of the present invention further comprising a commercially available fuel additive.

The ORI suppressing additive of the present invention is a reaction product obtained by reacting a hydrocarbon-substituted dibasic acid anhydride with a diamine having a block copolymer having a polyalkylene backbone. The hydrocarbon-substituted dianhydride reaction components used to obtain the reaction product additives of the present invention are of the following formula: or polymer components 0001-1 which are corresponding aminated or hydrogenated polymers or copolymers or mixtures thereof .0% by weight, preferably 0.01
~0.5% by weight of a mixture of hydrocarbons with boiling points ranging from 90 to below 450. In a preferred embodiment, the polymeric component is a mixture consisting mostly of polyisobutylene ethylenediamine and containing a small amount of polyisobutylene with a suitable amount of a hydrocarbon solvent. The automotive fuel composition of the present invention further comprises natural and synthetic lubricating oils of 0.
001 to 1.0, preferably 0.01 to 0.5% by weight.

The present invention also provides an additive concentrate comprising a hydrocarbon solvent together with 0.1-10.0% by weight of the reaction product components described above and 250-75.0% by weight of the polymer/copolymer hydrocarbon solvent mixture described above. relating to things. Concentrates of the invention exhibit improved storage stability and resistance to precipitation.

Referring now to the drawings, FIG. 1 shows the commercial fuel temperature (in the formula:
R1 is 500-10.000, preferably 500-2.000.
500, most preferably 600 to 1.500, e.g. 1
．． a hydrocarbon group having a molecular weight of 290, preferably a polypropenyl or polybutenyl group, most preferably a polyisobutenyl group; y has a value from 0 to 3).

When R3 is a preferred polyisobutenyl group,
y preferably has a value of 0, and therefore preferred hydrocarbon-substituted dianhydride reaction components for use have a value of the following formula: ) is a polyisobutenyl succinic anhydride. The polyisobutenyl succinic anhydride is most preferably composed of maleic anhydride and Amoco Gt+emicalComp.
The most preferred polybutene reactant is that commercially available as INDOPOL H-300. Methods of formulating the polyisobutenylsuccinic anhydride reactants described above are described, among others, in U.S. Pat.
No. 4,431°825 (Powell,
), No. 4.414.397 (Powell) and No. 4.325.876 (Chafetz).

The polyoxyalkylene diamine reactant used to prepare the reaction product component of the present invention has the following formula: groups, most preferably propylene or butylene groups: q and r are each integers having a value of 0 or 1, preferably q=l,
r-0: C is about 2-150, preferably 2-50
and b+d is about 2-150, preferably 2-5
has a value of 0; a+e is about 0 to 12, preferably 2 to
It is a diamine with a value of 8). In one embodiment, q=l, r
= and R2 is a butylene group, therefore the polyoxyalkylene diamine reactant has the following formula % where C has a value from 2 to 150, preferably from 2 to 50; b+d is 2 -150, preferably 2-50; a+e has a value of 2-12, preferably 2-8).

In another preferred embodiment, q=l, r=o, R2 is a propylene group, a+e has a value of O, and thus the polyoxyalkylenediamine reactant has the following formula % ( In the above formula, C and b+d are each 2 to 15
0, preferably 2 to 50). A polyoxyalkylene diamine of the above structure suitable for use is Texac.

Chemical Co, from Jeffamine E
Examples include those commercially available under the trade name of D series. Specific examples of such compounds are shown below.

The reaction product components of the present invention include 1.5 to 2.5 mole parts, preferably 2 mole parts, of a hydrocarbon-substituted dibasic acid anhydride and 0.5 to 2.5 mole parts, preferably 2 mole parts, of a polyoxyalkylene diamine reactant as described above.
1.5 mole part, preferably 1 mole part, from 30 to 200
C, preferably 90-150 C, by reaction until all water is removed from the system.

The reaction is preferably carried out in the presence of a solvent. Preferred solvents are those that are azeotropically distilled with water. Suitable solvents include hydrocarbons having a gasoline boiling range of about 30 to about 200<0>C. These include - for boat fishing, saturated and unsaturated hydrocarbons having from about 5 to about 10 carbon atoms. Examples of suitable hydrocarbon solvents include hexane, cyclohexane, benzene, toluene, and mixtures thereof. Xylene is the preferred solvent. The solvent can be present in an amount up to about 90% by weight of the total reaction mixture. Once the reaction is complete, the reaction product can then be separated from the solvent using conventional means or can remain mixed with some or all of the solvent.

The following examples demonstrate preferred methods of making the reaction products of the invention. It will be understood that the following examples are merely illustrative and are not intended to limit the invention in any way. In the examples, all parts are parts by weight, unless otherwise defined.

Polyisobutenylsuccinic anhydride (maleic anhydride and I
NDOPOL H-300), 779 parts of xylene, and 374.6 parts of polyoxyalkylene diamine were mixed at about 90 to 150°
The reaction was allowed to proceed at a temperature of C until no further water could be removed from the system. The polyoxyalkylene diamine has the following formula: % formula % where C has a value of about 40.5 and b+d is about 40.5.
5 and a+8 has a value of approximately 2.5). The reaction product was then filtered, stripped of residual solvent under reduced pressure, and identified by IRl NMR and elemental analysis.

Futane ± polyisobutenyl succinic anhydride (maleic anhydride and I
NDOPOL H-300), 4740 parts of xylene, and 2000 parts of polyoxyalkylene diamine were added to about 90 to 150 parts of polyoxyalkylene diamine.
The reaction was allowed to take place at a temperature of 0.degree. C. until no more water could be removed from the system. Polyoxyalkylene diamine (Jeffamine ED-20011 has the following formula:
).

Example 1 illustrates a preferred method of preparation and preferred reaction product components of the present invention. Herein, the active portion of the reaction product composition of Example 1 has the following formula: is assumed to be a bis-polyisobutenyl succinimide with a structure of

The optional polymer component of the motor fuel compositions of the present invention is a C2 to C1 degree hydrocarbon polyolefin polymer, copolymer or corresponding aminated or hydrogenated polymer or copolymer or mixtures thereof. Such polymer/copolymer components may have a molecular weight of about 500 to 10,000, preferably from 500 to 3,500, most preferably from about 650 to 2,000.
, 600. Mixtures of olefin polymers having average molecular weights within the ranges mentioned above are also useful. - For boat fishing, the olefin monomer from which the polyolefin polymer component is produced is preferably an unsaturated C2-C6 hydrocarbon. Specific examples of olefins that can be used to make the polyolefin polymer component include ethylene, propylene, isopropylene, butylene, isobutylene, amidino, hexylene, butadiene, and isoprene. Propylene, isopropylene, butylene and isobutylene are particularly preferred for use in making the polyolefin polymer component. Other polyolefins that can be used are those obtained by decomposing high molecular weight polyolefin polymers or copolymers into polymers in the molecular weight ranges mentioned above. Derivatives of the above polymers obtained by saturation by hydrogenation or amination of the polymer to produce polymeric mono- or polyamines are also useful and form part of the invention. As used herein and in the appended claims, the term "polymer" is intended to include polyolefin polymers and their corresponding hydrogenated or aminated derivatives. The optional polymeric component is typically used in admixture with a hydrocarbon solvent to facilitate addition into the base motor fuel composition.

In one preferred embodiment of the invention, the optional polymer component is polypropylene having an average molecular weight of 750 to 1000, preferably about 800.

In other preferred embodiments, the optional polymer component has a molecular weight of 1000 to 1500, preferably about 1
It is a polyisobutylene with an average molecular weight of 300.

In yet another preferred embodiment of the invention, the optional polymeric component is mixed with a suitable amount of a hydrocarbon solvent and is a mixture consisting predominantly of polyisobutylene ethylene diamine with a small amount of polyisobutylene. . In this embodiment, the polyisobutylene ethylene diamine component in the optional polymer component is typically 50 to 75 parts by weight, preferably about 60 parts by weight, based on the weight of the total composition comprising the polymer component.
Present in a concentration of parts by weight. The polyisobutylene ethylenediamine component is of the following formula: H3CH3CH3CH3cn3, where Z has a value of 10 to 40, preferably 30 to 35, for example 33.

The polyisobutylene component in the optional polymer component is usually 5 to 25 parts by weight, preferably 10 to 20 parts by weight, based on the weight of the total composition making up the polymer component.
Present in a concentration of parts by weight.

The polyisobutylene component has the following formula: % formula %: (In the above formula, Z is 10 to 40, preferably 30 to 3
5, for example 33).

The hydrocarbon solvent used to facilitate the addition of the optional polymeric component into the base automotive fuel composition may include:
Preferably it is a light aromatic distillate composition. A commercially available light aromatic distillate composition comprising the above-described polyisobutylene ethylene diamine and a polyisobutylene compound at the concentrations defined above, and therefore most preferred for use as the optional polymer component of the present invention, comprises (j
+Gasoline additive 0RONITE 0GA commercially available from evron Chemical Company
-472. 0RONITEOGA-472 contains about 60 parts by weight of polyisobutylene ethylene diamine, about 13 parts by weight of polyisobutylene, and about 2 parts by weight of light aromatic distillates including xylene and C9 alkylbenzenes.
7 parts by weight. 0RONITE 0GA
Fuel compositions containing -472 as an additive include U.S. Pat.
No. 3,966.429.

The motor fuel composition of the present invention consists mostly of the base motor fuel and contains from 0.0005 to 5.0% by weight, preferably from 0.001 to 1.0% by weight of the reaction products described above. The fuel optionally also contains 0.001-1.0% by weight, preferably 0.01-0.5% by weight of the optional polymeric components described above. Preferred base automotive fuel compositions are for use in spark ignition internal combustion engines. - Such motor fuel compositions, referred to as gasoline-based materials for boat fishing, preferably have an angle of about 90° to about 450°
It is preferred to include a mixture of hydrocarbons having a boiling point in the gasoline boiling range of F. The base fuel may consist of straight-chain or branched paraffins, cycloparaffins, olefins, aromatic hydrocarbons or mixtures thereof. The base fuel can be derived from straight-run naphtha, polymer gasoline, natural gasoline or catalytically cracked or pyrolyzed hydrocarbons and catalytically regenerated feedstocks, among others. The composition and octane value of the base fuel is not critical, and any conventional motor fuel may be used in the practice of this invention. An example of the automotive fuel composition of the present invention is shown below in Example 3.

Example 11 30 PTB of the reaction product shown in Example 1 (i.e., 30 bonds of reaction product per 1000 barrels of gasoline; equivalent to about 0.01% by weight of reaction product based on the fuel composition) was subjected to aromatic carbonization. Consisting of 22% hydrogen, 11% olefinic hydrocarbons and 67% paraffinic hydrocarbons, approximately 9%
A bulk base motor vehicle fuel that is essentially lead-free (less than 0.05 g tetraethyl lead per gallon) special grade gasoline containing a mixture of hydrocarbons having a boiling point in the gasoline boiling range of 0 to 450 below, where: It was blended with base fuel A).

The ORI trend of base fuel A containing the commercially available fuel additive 60 PTB (60 bonds of reaction products per 1000 barrels of gasoline, equivalent to approximately 0.02% by weight of reaction products based on the weight of the fuel composition) was compared to the inventive enrichment. The ORI trends of automotive fuel compositions containing the following were determined in an engine cleanliness test, as shown in Example 4 below.

Backing 1 30 PTB of the reaction product shown in Example 1 (i.e., 30 pounds of reaction product per 1000 barrels of gasoline; equivalent to about 0.01% by weight of reaction product based on the fuel composition), and polyisobutylene ethylene diamine. Approximately 60
parts by weight, about 13 parts by weight of polyisobutylene, and about 27 parts by weight of a light aromatic distillate containing xylene and C9 alkylbenzene (ORONITE 0GA-4).
721205.5PTB (approximately 0.07% by weight) at 10
0 veil oil.

In the engine cleaning test, commercially available fuel additive 60P
The ORI trend of base fuel A containing TB was measured in a 1983 Chevrolet 2.0β multi-cylinder engine (throttle body injector). The engine was a Siboshi 2.02 in-line four-cylinder engine with cast iron alloy cylinders with separate intake and exhaust ports for each cylinder. The electronically controlled fuel injection system controls various engine operating parameters (e.g. manifold absolute pressure,
The required fuel flow to each engine cylinder was maintained by monitoring throttle valve position, coolant temperature, engine speed, and exhaust gas oxygen content and adjusting fuel flow accordingly. The fuel system that supplies fuel to the engine was specifically adapted to measure engine ORI. At the beginning of the engine testing process, a fuel with a sufficiently high octane value was used that no engine knocking was observed. This fuel was then replaced with the next lower octane fuel and this process continued until knocking was observed. The octane value that is one value higher than the knocking state is the octane requirement of the engine.

The engine ORI for an automotive fuel composition containing base fuel A and commercially available additive 60 PTB was determined for 200 engine operating hours.
measured as a function of engine operating time, up to
Next, the engine was disassembled and inspected. The engine is then reassembled and stabilized, at which point the concentrated composition of the present invention (as exemplified in Example 4) is added to the composition containing base fuel A and commercially available fuel additive 60 PTB. Introduced.

As shown in FIG. 1, the octane requirement of the engine using commercially available gasoline was approximately 92 at the time the engine was disassembled. After reassembling the engine, restabilizing it, and introducing the concentrate of the present invention, the engine's octane requirements will be:
The value decreased from a value of about 92 at 300 hours of engine operation to a value of about 87 at 400 hours of engine operation. Accordingly, the results shown in Figure 1 indicate that the automotive fuel composition of the present invention has a lower ORI tendency compared to conventional commercial gasoline.

In addition, O of base fuel A containing 60 PTB of commercially available fuel additive
The RI trends and ORI trends of an inventive automotive fuel composition (exemplified in Example 5 below) further comprising the commercially available fuel additive 60 PTB were compared in an engine cleanliness retention test.

120 ppm of the reaction product shown in Example 1
(approximately 0.01% by weight), commercially available fuel additive 60PTB (
about 60 parts by weight of polyisobutylene ethylene diamine, about 13 parts by weight of polyisobutylene, and about 27 parts by weight of a light aromatic distillate containing xylene and C9 alkylbenzene (ORONIT);
E OGA-4721822ppm (approximately 0.07% by weight
) was prepared into an automotive fuel composition.

For the Engine Cleanliness Test, engine octane requirements for a 1983 Cipollet 2012 engine (throttle body injector) were measured using equipment similar to that described for the Engine Cleanliness Test. The experimental results obtained from the cleanliness retention test on base fuel A containing the commercially available fuel additive 60 PTB and the composition of the present invention (exemplified in Example 5) are shown in FIG. As shown by FIG. 2, the octane requirement of an engine using base fuel A containing commercially available fuel additive 60 PTB is the same as the corresponding octane requirement of an engine using the automotive fuel composition of the present invention (Example 5). was consistently higher throughout the elapsed time of the study. Accordingly, the results shown in FIG. 2 demonstrate that the automotive fuel compositions of the present invention have advantages over commercially available fuel compositions in controlling engine ORI.

It has also been found that the automotive fuel composition of the present invention is effective in preventing deposits from accumulating in the carburetor, intake manifold, and intake valve of an internal combustion engine. The carburetor intake valve and intake manifold cleaning properties of commercially available automotive fuel and the automotive fuel composition of the present invention (Example 5) were evaluated in an excellence evaluation test (
Merit Rating Te5t). This test can be shown as follows. With a given automotive fuel composition, 2. C1! After the engine was operated, a portion of the engine was disassembled and various engine parts were visually inspected to determine the extent of deposit formation. This is measured by a visual rating system on a scale of 1-10. Here, a value of 10 means that the part is clean, and a value of 1 means that the part has deposits.

Table 1 shows the experimental results obtained from the excellence evaluation test. As shown by Table 1, the automotive fuel composition of the present invention (Example 5) is about as effective as commercially available fuels (based on excellence ratings), and also has an improved valve composition. showed adhesion control.

For convenience of transportation and handling, it is useful to prepare concentrates of the reaction products, either alone or in conjunction with the optional polymeric components of the present invention. Concentrates can be prepared in suitable liquid solvents such as toluene and xylene, with xylene being the more preferred solvent. In a preferred embodiment of preparing the concentrate of the present invention, 10% by weight of the reaction product of Example 1 is used, preferably 5.0-10% by weight.
0.0% by weight and the aromatic distillate/polyisobutylene ethylenediamine/polyisobutylene mixture described above,
Aromatic hydrocarbon, preferably xylene 25.0-50.
0% by weight, preferably 30.0 to 40.0% by weight. Here, all weight percentages are based on the total weight of the concentrate. As noted above, the concentrated compositions of the present invention are advantageous in that the concentrated compositions of the present invention prevent precipitation and can therefore be more easily stored and transported. ,354
(Sung et al.)
It has advantages over I-controlled concentrated formulations.

The motor fuel and concentrate compositions of the present invention may further include any additives commonly used in motor fuel compositions. Accordingly, the composition of the present invention may further contain conventional carburetor cleaners, anti-knocking agents such as tetraethyl lead compounds, antifreeze agents, upper cylinder lubricants, and the like. In particular, such further additives may include polyolefin polymers, copolymers or corresponding hydrogenated polymers or copolymers of 02-C6 unsaturated hydrocarbons or mixtures thereof. Further additives may also include substituted or unsubstituted mono- or polyamine compounds, such as alkylamines, ether amines and alkyl-alkylene amines or blends thereof.

In another preferred embodiment, the motor fuel composition of the invention further comprises from 0.001 to 1.0, preferably from 0.01 to 0.5% by weight of a natural or synthetic lubricating oil. Lubricating oils suitable for use in the automotive fuel compositions of the present invention include:
For example, U.S. Pat. No. 4.670, which is hereby incorporated by reference.
, No. 173 (Hayashi et al.), columns 29-30, examples include natural oils such as animal oils and vegetable oils, inorganic lubricating oils (e.g. liquid petroleum oils, paraffinic oils, naphthenic oils). and paraffinic/naphthenic mixed type solvent-treated or acid-treated inorganic oils) and lubricating oils derived from shale or coal.

Synthetic oils suitable for use include hydrocarbon oils, octoday-substituted hydrocarbon oils, such as polymerized and copolymerized olefins, oligoalkenes, alkylbenzenes, polyphenyls, alkylated diphenyl ethers and sulfides,
and substituted and unsubstituted alkylene oxide polymers and copolymers, such as oils made by polymerizing ethylene oxide or propylene oxide,
Alkyl and aryl ethers of these polyoxyalkylene polymers, or polycarboxylic esters thereof, such as acetic acid or fatty acid esters).

Particularly preferred types of synthetic lubricating oils for use include esters and polyesters of mono- and dicarboxylic acids and mixtures thereof.

Other types of oil that are particularly preferred for use are unrefined or refined heavy oils. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. Refined oil is similar to unrefined oil, but is further treated in one or more refining steps to improve one or more properties. Many such purification methods (eg, solvent extraction, secondary distillation, acid or base extraction, filtration, percolation) are well known to those skilled in the art.

The present invention also relates to a method of incorporating the reaction product composition, either alone or in combination with the optional polyolefin polymer/copolymer components described in item 1, into a base motor fuel composition. The blending method is approximately 90-450
0.0005 to 5 of the reaction product of the present invention as described in 1.
0% by weight, preferably o,ooi to 1.0% by weight. The reaction product may be introduced directly into the hydrocarbon-based fuel or may be first mixed with a hydrocarbon solvent such as xylene, toluene, hexane, cyclohexane, benzene, and mixtures thereof.

When using a polyolefin polymer/copolymer component, the above-described compounding method can be applied to the above-described reaction product 0.
．． 0005 to 5.0, preferably 0.001 to 1.0% by weight and the polyolefin polymer/copolymer component as described above 0.001 to 1.0, preferably 001 to 0.5
% by weight into the base fuel. The polymer/copolymer component may be introduced directly into the hydrocarbon-based fuel or may be mixed first with a hydrocarbon solvent such as toluene, xylene or c2-Cto alkylbenzene.

In another embodiment of the above-described formulation process, the inventive concentrate as described above, i.e., a concentrate comprising the above-described reaction product, alone or optionally in combination with a polyolefin polymer/copolymer component, is added to the base fuel. This is done by introducing

[Brief explanation of the drawing]

FIG. 1 shows a 2.5-mt. Cl! The octane requirement of the engine (as a function of engine operating time) was compared with the octane requirement of the same engine after it was disassembled, reassembled, stabilized, and the composition of the invention was introduced. FIG. 2 shows the octane demand (as a function of engine operating time) of a Sibosee 2.0°C engine using a commercially available unleaded base fuel containing (il commercial fuel additive 60 PTB) and (ii
FIG. 1 shows data obtained comparing the octane requirements of the same engine using a motor vehicle fuel composition of the present invention further comprising a commercially available fuel additive.

Claims (8)

[Claims] (1) A method for producing an automobile fuel additive by reacting dicarboxylic acid anhydride and polyamide, (a) The following formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is 500 to 1.5 to 2.5 mole parts of a hydrocarbon-substituted dibasic acid anhydride (a hydrocarbon group having a molecular weight of 10,000, and y is 0 to 3), and (b) the following formula: ▲ Formula, There are chemical formulas, tables, etc. and a+e is 0 to 12) with 0.5 to 1.5 mol parts of polyoxyalkylene diamine at a temperature of 30 to 200°C. (2) such hydrocarbon-substituted dibasic acid anhydride reactant is
The method according to claim 1, wherein the polyisobutenyl succinic anhydride is a polyisobutenyl succinic anhydride having the following formula: ▲A mathematical formula, a chemical formula, a table, etc.▼ (wherein x has a value of 10 to 30). (3) The polyoxyalkylene diamine reactant has the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Or the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, c is about 2 to 50, and b+d is approximately 2
50 and a+e is about 2-8). (4) characterized in that it contains 0.0005 to 5.0% by weight of the product of the method according to any one of claims 1 to 3;
A motor fuel composition comprising a mixture of hydrocarbons having a boiling point in the range of 32-232°C (90-450°F). (5) Olefin polymers from 0.001 to 0.001 with a molecular weight of 500 to 10,000, selected from homopolymers and copolymers of C_2 to C_1_0 olefinic hydrocarbons, corresponding aminated or hydrogenated polymers or copolymers, or mixtures thereof. 5. The composition of claim 4 further comprising 1.0% by weight. (6) The olefin polymer component is a hydrocarbon solvent, and (a) 50 to 75 parts by weight of polyisobutylene ethylene diamine of the following formula: The automobile fuel composition according to claim 5, which is a mixture containing 5 to 25 parts by weight of polyisobutylene represented by a mathematical formula, a chemical formula, a table, etc. ▼ (in the above formula, z is 10 to 40). (7) The motor fuel composition according to any one of claims 4 to 6, further comprising 0.001 to 1.0% by weight of a natural or synthetic lubricating oil. (8) A motor fuel additive concentrate composition comprising a hydrocarbon solvent and an additive, wherein said additive comprises (I) 0.1 of the product of the process of any one of claims 1-3. ~10.0% by weight, and (II) a hydrocarbon solvent, and (a) 50 to 75 parts by weight of polyisobutylene ethylenediamine of the following formula: Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, z is 10 to 40) A mixture containing 5 to 25 parts by weight of polyisobutylene 25.
A composition comprising 0 to 75.0% by weight.